CN1913777B - Synergistic antifungal DDAC compositions - Google Patents
Synergistic antifungal DDAC compositions Download PDFInfo
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- CN1913777B CN1913777B CN2005800040135A CN200580004013A CN1913777B CN 1913777 B CN1913777 B CN 1913777B CN 2005800040135 A CN2005800040135 A CN 2005800040135A CN 200580004013 A CN200580004013 A CN 200580004013A CN 1913777 B CN1913777 B CN 1913777B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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Abstract
The present invention relates to synergistic antifungal compositions comprising didecyl ammonium chloride (DDAC) and a post-harvest antifungal agent selected from the group consisting of imazalil, boscalid, fenhexamid, pyrimethanil, thiophanate-methyl, triflumizole, azoxystrobin, dimoxystrobin,picoxystrobin, and pyraclostrobin for protecting plants, fruit or seeds against phytopathogenic fungi.
Description
The present invention relates to a kind of collaborative antifungal composition; it contains didecyl ammonium chloride (DDAC) and be protective plant after results; the antifungal agent of the anti-plant pathogenic fungi of fruits and seeds; but this antifungal agent comprises mould azoles (imazalil); Boscalid (boscalid); fenhexamid (fenhexamid); phonetic mould amine (pyrimethanil); thiophanate-methyl (thiophanate-methyl), fluorine bacterium azoles (triflumizole); Fluoxastrobin (azoxystrobin); ether bacterium amine (dimoxystrbin); ZEN 90160 (picoxystrobin) and pyraclostrobin (pyraclostrbin).
The antifungal combination agent comprises that the antifungal agent that uses behind the crop harvesting presses down mould azoles, phonetic mould amine or thiabendazole disclose in WO-99/12422, this patent has been described the synergistic composition that presses down mould azoles and fluorine ring azoles, the WO-03/011030 patent has been described Fungicidal composition, comprises phonetic mould amine and presses down mould azoles.WO-98/56366 discloses the composition that is used as anti-microbial agents, comprises a kind of quaternary ammonium compound and a kind of guanidinesalt composition.
Have now found that; in the certain limit of composition (promptly certain ratio separately or the amount of active ingredient); be that industry those skilled in the art are easy to the amount with regard to detecting; with the antifungal agent behind DDAC (hereinafter to be referred as Compound I) and a kind of crop harvesting; be selected from and press down mould azoles; Boscalid; fenhexamid; phonetic mould amine; thiophanate-methyl; fluorine bacterium azoles; Fluoxastrobin; ether bacterium amine; ZEN 90160 and pyraclostrobin (hereinafter to be referred as Compound I I) combination; can provide a kind of synergistic function in control during plant pathogenic fungi, promptly antimycotic plant; synergy control of growing on the fruits and seeds or synergy protective effect.
DDAC, promptly Compound I is being commonly called as of DDAC, available following formula representative
DDAC has bactericidal activity, is used to extensive fields: be disinfectant, and the active ingredient of sanitizer and hospital, family, laundry, farm and the used cleaning agent of industrial circle; It is the water treatment biocide of cooling tower and secondary oil recovery; It is the bactericide that the protection textile is avoided the permanent pollution of der Pilz fungi; Be to prevent the active ingredient of the solution of timber decolouring conk for the good timber of new saw provides temporary protection.
Mycocidal composition (II) is after being used for crop harvesting: press down mould azoles; composition (II-a); be a kind of the have protection and fungicide of therapeutic action, be used to prevent and treat the far-ranging fungi that encroaches on fruit, vegetables and ornamental plants, comprise that the stain of the white powdery mildew of cucumber and rose is mould.Press down mould azoles also be used to soak seed and handle after the harvesting oranges and tangerines, banana and other fruit in case storage period rot.Pressing down mould azoles is compound 1-[2-(2,4 dichloro benzene base)-2-(2-propenyloxy group) ethyl]-trade name of 1H-imidazoles, this compound can be represented with following formula
Boscalid, composition (II-b) is a leaf fungicide, the powder that is used to prevent and treat fruits and vegetables is mould, Alternaria, botrytis sp, sclerotinite is mould and clump stalk spore is mould.Boscalid is the trade name of compound 2-chloro-N-(4 '-chlordiphenyl-2-yl)-vitamin PP, and this compound can be represented with following formula
Fenhexamid, composition (II-c) is a leaf fungicide, is used to prevent and treat mould, mould with the relevant disease fungus of clump stalk spore of light grey and pinkish spore of grape, berry, nut, oranges and tangerines, vegetables and ornamental plants.Fenhexamid is the trade name of compound 2 ', 3 '-two chloro-4 '-hydroxyl-1-hexahydrotoluene carbonyl anilide, and this compound can be represented with following formula
Phonetic mould amine, composition (II-d) is a kind of fungicide with protection and therapeutic action, the gray mold that is used for preventing and treating liane, fruit, vegetables and ornamental plants.Said composition (II-d) is a compound 4, the trade name of 6-dimethyl-N-n-phenyl-2-pyrimidine-amine, and this compound can be represented with following formula
Thiophanate-methyl, composition (II-e) is a kind of fungicide with protection and system of therapeutic action, is used for processing and seed soaking behind the crop harvesting, to kill diversified disease fungus.Thiophanate-methyl is a compound 4, the trade name of 4 '-(right-phenylene) two (3-thiourea carbamates), and this compound can be represented with following formula
Fluorine bacterium azoles, composition (II-f) is compound (E)-4-chloro-α, α, the trade name of α-three fluoro-N-(1-imidazoles-1-base-2-propoxyl group ethylidene)-right-toluidines, this compound can be represented with following formula
Fluorine bacterium azoles is a kind of antifungal protective agent that is used for soil spray, foliage spray or irrigation (chemigation), is used in the mycosis of the ornamental plants of (as greenhouse, booth and indoor) growth in the control enclosed construction.
Fluoxastrobin, composition (II-g) is a kind of fungicide with system of protection, control, elimination, disconnected leaf character, the mycosis that is used to prevent and treat cereal, vegetables and fruit.Fluoxastrobin is methyl (E)-2-[2-[6-(2-cyano group-phenoxy group) pyrimidine-4-base oxo] phenyl]-trade name of 3-methoxy acrylate, this compound can be represented with following formula
Ether bacterium amine; composition (II-h); be a kind of have protection, control and disconnected leaf character; be used to prevent and treat the mycotic fungicide of cereal, vegetables and fruit; it is (E)-2-(methoxyimino)-N-methyl-2-[α-(2; 5-xylyl oxo)-and p-methylphenyl] trade name of acetamide, this compound can be represented with following formula
ZEN 90160; composition (II-i); be a kind ofly to have protection and prevent and treat character; be used to prevent and treat the mycotic fungicide of cereal, vegetables and fruit; it is (E)-3-methoxyl group-2-[2-(6-trifluoromethyl-2-pyridine oxygen base-methyl) phenyl] trade name of acrylate, this compound can be represented with following formula
Pyraclostrobin; composition (II-j); be a kind of have protection, control and disconnected leaf character; be used to prevent and treat the mycotic fungicide of cereal, vegetables and fruit; it is the trade name of methyl N-(2-[1-(4-chlorphenyl)-1H-pyrazole-3-yl oxo valency base] phenyl) (N-methoxyl group) carbamate, and this compound can be represented with following formula
The antifungal agent that is used for behind the crop harvesting presses down mould azoles (II-a), Boscalid (II-b), fenhexamid (II-c), phonetic mould amine (II-d), thiophanate-methyl (II-e), fluorine bacterium azoles (II-f), Fluoxastrobin (II-g), ether bacterium amine (II-h), ZEN 90160 (II-i) and pyraclostrobin (II-j) can its free alkali form or exist with a kind of form of acid-addition salts, acquisition is reacted in the form of latter's available bases and a kind of suitable acid.Suitable acid comprises inorganic acid, as halogen acids, i.e. and hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, nitric acid, phosphonic acids, phosphinic acids or the like; Perhaps organic acid, as acetate, propionic acid, glycolic acid, 2 hydroxy propanoic acid, 2-oxo propionic acid, ethanedioic acid, malonic acid, succinic acid, (Z)-the 2-butene dioic acid, (E)-the 2-butene dioic acid, the 2-hydroxysuccinic acid, 2,3-dyhydrobutanedioic acid, 2-hydroxyl-1,2,3-propyl group tricarboxylic acids, methanesulfonic acid, ethyl sulfonic acid, benzene sulfonic acid, the 4-toluene sulfonic acide, cyclohexylsulfamic acid, 2-hydroxy benzene sulfonic acid, 4-amino-2-hydroxy benzene sulfonic acid or the like.
The form that presses down the specific salt of mould azoles (II-a) is sulphate, phosphate, acetate, nitrate or phosphite.
The form of the specific salt of phonetic mould amine (II-d) is phonetic mould amine oleate.Other phonetic mould amine salt, for example malonate and phthalate etc. had been described as compound (2)～(13) the 3rd page of WO-97/40682.
The composition of in composition, using among the present invention (I) and (II) preferably exist with pure in fact form, promptly do not contain the chemical impurity (as joint product or remaining solvent) that in its production or transportation, produces, so that monitor the plant pathogenic fungi administration project safely.The used term " pure in fact " in front means the conventional method with this ambit, detect the purity (purity of chemistry or the purity of optics) that obtains as high performance liquid chromatography or optical means and reach 96% at least, preferably reach 98% at least, more preferably reach 99% at least.
Pressing down mould azoles (II-a) has an asymmetric carbon atom, is with two kinds of enantiomeric mixture therefore, particularly with the form of racemic mixture, or is used in the composition that is embodied with a kind of pure in fact (R)-or (S)-enantiomter.Used " pure in fact " means the conventional method with this ambit in the front, detect the purity (purity of chemistry or the purity of optics) that obtains as high performance liquid chromatography or optical means and reach 96% at least, preferably reach 98% at least, more preferably reach 99% at least.
Composition of the present invention is the fungicide of the anti-plant pathogenic fungi of wide spectrum.This class fungi can be enumerated Ascomycetes (Erysiphe, chain sclerotinia sclerotiorum belongs to, Uncinula, Aureobasidium refers to Phytophthora for Venturia for example, Podosphaera); Basidiomycetes (for example hunchbacked spore Rust, Rhizoctonia, Puccinia, cellar fungus belongs to, and buries Peziza, and transverse hole fungus belongs to, Uromyces, sticking gill fungus belongs to, Lentinus, Coriolus Qu61, rake Pseudomonas); Fungi impertecti (for example Botrytis, Helminthosporium, Rhynchosporium spp, Fusarium, Septoria, Cercospora, Alternaria, Penicillium, Geotrichum).
In the composition of reality, composition (I) is cooperated with a kind of relative ratio with a kind of composition (II), it is synergistic antimycotic, the effect of particularly anti-plant, fruit and seed disease fungal pathogens has only composition (I) or has only the anti-mycotic efficiency of composition of active ingredient of a kind of composition (II) beyond thought good compared with the sort of.This professional people knows just as being familiar with, composition in the composition (I) and composition (II) can be matched with various ratios, thereby obtain so-called synergistic action effect, the ratio of composition in the composition (I) and composition (II) is decided by the fungal species that will prevent and treat and handle.Based on current prompting in application, whether the ratio of measuring composition in these compositions (I) and composition (II) has collaborative killing action to specific fungi is the routine work of being familiar with these professional personnel.Yet,, we can say that composition in the composition (I) is 1: 100～10: 1 to the suitable ratio (weight ratio) of composition (II), is more preferably 1: 50～2: 1 as a total principle to most of plant pathogenic fungis.
According to the present invention, the amount of every kind of active component will be such in the composition, can obtain a kind of synergistic fungicidal effect.The amount of wishing composition in the composition of the present invention (I) especially is 10～1000mg/L.The amount of composition (II) is decided by the sp act of selected composition (II), and scope also is 10～1000mg/L.For example composition (II-a) promptly presses down mould azoles, and its amount is exactly 10～1000mg/L, preferably 500mg/L.
Composition among the present invention comprise can provide a kind of collaborative antifungic action with the collocation of various ratios as the DDAC of composition (I) with as the antifungal agent behind the crop harvesting of composition (II), and one or more adoptable carriers.But composition wherein (II) comprises mould azoles (II-a), Boscalid (II-b), ring acyl mattress amine (II-c), phonetic mould amine (II-d), methyl sulphur mattress spirit (II-e), fluorine mattress azoles (II-f), Fluoxastrobin (II-g), ether bacterium amine (II-h), ZEN 90160 (II-i), and pyraclostrobin (II-j).
These carriers can be any materials, generated by composition (I) and the composition that (II) constitutes with these carriers, use to impel in the place of needs treatment/or propagate these compositions, for example dissolving, allot or disperse said composition, and/or impel its storage, transportation or dispose and do not weaken its antimycotic effect.Said adoptable carrier can be solid-state, also can be liquid, or a kind of gas that has been compressed liquefaction.Be that this composition of the present invention is suitable as concentrate, emulsion, emulsible concentrate; The concentrated suspension that oil is molten, the soluble liquid that oil is molten, solubility concentrates thing, solution, particulate, pulvis sprays dust, propellant, aerosol, pill or pulvis.
The Fungicidal composition that the preparation of available in many cases mother liquor is directly used, emulsifier mother liquor for example, suspending agent mother liquor, or the mother liquor of solubility, water or organic media dilute, and these mother liquors all are that the composition that defines of the present invention is involved.These mother liquors can be diluted to before reality is used and can be contained in the sprayer the i.e. mixture of usefulness.Preferably, should contain the composition (I) of 0.01～95% (weight ratio) and (II) in the composition of the present invention.Preferred, this proportion is 0.1～90% (weight ratio).Most preferred, this proportion is 1～80% (weight ratio), and described in following detailed annotation, this will depend on the type of the prescription that is elected to be special-purpose.
The emulsifier mother liquor is composition (I) and formulation liquid state (II), homogeneous, becomes emulsion behind the dilute with water and uses.The suspending agent mother liquor is the stable suspending agent type of active component in a kind of liquid, dilute with water before use.The solubility mother liquor is a kind of formulation of liquid homogeneous, and a kind of true solution as active component behind the dilute with water uses.
Fungicidal composition of the present invention also can be made into cerate, and the surface that spreads upon some fruit, particularly citrus fruit forms protective layer.
But Fungicidal composition of the present invention have protective plant, fruit and seed help treat, Fungicidally active that prevention and anti-spore generate.These present mixtures can be used to certain position of protective plant or plant; for example fruit, flowers, flower, leaf, limb, root, transplant, stem tuber, ornamental plants etc.; make it avoid infection by microorganisms, infringement or destruction, and the longer afterwards plant part of protection is not subjected to the infringement of these microorganisms.
Because the suitable cultivated plant of composition of the present invention (I) and composition (II) is of a great variety, can classify as cereal to them, wheat for example, barley, rye, oat, rice, Chinese sorghum or the like; The beet class is as preserved carrot and fodder beet; Fruit, nut and soft fruits are as apple, pears, plum, peach, apricot, cherry, strawberry, rasp berry and blackberry, blueberry; Leguminous plant, for example green soya bean, lentil, pea, soybean; Oil plants is as grape, mustard seed, opium poppy, olive, sunflower, coconut, castor oil plant, cocoa, peanut; Plant cucurbitaceous is as pumpkin, cuke, watermelon, cucumber, pumpkin; Fibre plant such as cotton, flax, hemp, jute; Oranges and tangerines section fruit is as orange, lemon, grapefruit, oranges and tangerines; Greengrocery is as spinach, lettuce, asparagus, Chinese cabbage, as cabbage and radish, carrot, onion, tomato, potato, pepper and black pepper; Bay class plant, for example avocado, cinnamon, camphor tree; Or some plants like this, as corn, tobacco, peanut, coffee, sugarcane, tea, grape, golden hop, banana, bamboo grows, and ornamental plants, as the evergreen tree of flowers, shrub, deciduous tree and coniferous tree and so on.List these cultivated plants just for the present invention is described, range of application of the present invention is not limited to this.
An AD HOC using antifungal composition of the present invention is the acrial part that it is used in plant, particularly is used on the leaf of plant (foliage applying).Number of times of using and dosage will meet biology characteristics and the weather conditions of protected plant.This antifungal composition also can be applied in the soil, in case liquid composition has been sprayed at certain position of plant, or this composition made the soil formulation, as make the granule of using in the soil and be applied in the soil, enter (systemic activity) in the plant corpus after will absorbing by root system.
Antifungal composition of the present invention is particularly suitable for handling fruit, the especially citrus fruit after the results.Under latter event, available a kind of liquid formulation is sprayed to fruit, or fruit is immersed in this liquid formulation, perhaps is coated with a wax layer with a kind of cerate composition to fruit.This cerate composition in back easily prepares, and is about to a kind of suspending agent mother liquor and a kind of suitable wax and fully mixes.The formulation that is used to spray and soaks can be diluted with a kind of aqueous medium with emulsifier mother liquor, suspending agent mother liquor or soluble liquid and be prepared.In most of the cases this class mother liquor all by active component, dispersant or suspending agent (surfactant), thickener, a spot of organic solvent, humidizer, antifreezing agent and water constitute arbitrarily for some.
Fungicidal composition of the present invention also can be used for protecting seed to avoid the fungi infringement.For bringing into play this effect, available Fungicidal composition of the present invention is coated with one deck " coat " for these seeds, in this case, the seed of cereal can soak with the fluid composition that contains active component in proper order, perhaps gives seed coating with the composition that merged in the past.
To the composition (I) of this merging and (II), preferably use with the form of composition, wherein two kinds of compositions are admixed together fully to guarantee that these two kinds of compositions throw simultaneously to claimed thing.Throw or use composition (I) and (II) also can take the mode of " one after another-merge " to offer medicine or medication, promptly be used alternatingly or use one after another composition (I) and composition (II) in same place, Tou Yao prerequisite is by this way, and these two kinds of compositions must mix fully in handled place.If in very short time, for example in 24 hours, or preferably in 12 hours dispensing or medication just can accomplish this point.This method that is used alternatingly can be carried out like this, for example uses a kind of suitable unitary package, has the composition that is filled with a kind of active component (II) in the container in this packing at least.Therefore the present invention also comprises a kind of like this product, it contains :-(a) a kind of composition (being DDAC) that contains composition (I), with-(b) a kind of composition that contains composition (II), composition (II) can be to press down mould azoles (II-a), Boscalid (II-b), fenhexamid (II-c), phonetic mould amine (II-d), thiophanate-methyl (II-e), fluorine bacterium azoles (II-f), Fluoxastrobin (II-g), ether bacterium amine (II-h), ZEN 90160 (II-i), and pyraclostrobin (II-j), these two kinds of compositions use together simultaneously or successively order use, said here composition (I) and (II) shared separately ratio can form a kind of synergy to kill plant pathogenic fungi.Such product can be a kind of suitable packing, and the container that separates is separately wherein arranged, and a kind of of composition (I) or composition (II) is housed in each container, preferably all with the form of preparation.This class dosage form is general all just like the described same composition that contains two kinds of active ingredients simultaneously of preparation.
Be used for the present composition suitable carriers and the batching can be solid or liquid, and with this area in the suitable material known be complementary, for example natural or regenerate mineral matter, solvent, dispersant, surfactant, wetting agent, binder, intensifier, adhesive, fertilizer or antifreezing agent.
Except above-mentioned composition (I) and (II), can also comprise other active component in the composition of the present invention, for example other bactericide, particularly fungicide, and insecticide, miticide, nematocide, weed killer herbicide, plant growth regulator and fertilizer.
Composition (I) and form that (II) can consistency are used, and perhaps, preferably the dispersant that can easily find in formulation art uses.So they have just become preparation, form the emulsifier mother liquor by method well known in the art, solution that can directly spray or dilutable, the emulsifier of dilution, wetting powder, soluble powder, pulvis, granule, and the capsule preparations of making of polymer.According to the different in kind of composition, according to the purpose that will reach and main situation, can select different usings method, for example spray, spray, dust, spread or topple over etc.
These preparations, be these compositions, prepared product or mixture all be with the method for knowing in this area (for example homogeneity mix and/or with incremental agent (solvent for example, solid carrier and surfactant) grind active ingredient together) preparation, all contain these active components, and contain dispersant a kind of solid or liquid at suitable place.
Suitable solvent is an aromatic hydrocarbon, preferably contains the aromatic hydrocarbon of 8～12 carbon atoms, for example the naphthalene of xylene mixture or replacement; Phthalate, for example dibutyl phthalate or dioctyl phthalic acid ester; Aliphatic hydrocarbon or clicyclic hydrocarbon, for example cyclohexane or paraffin; Alcohols and di-alcohols and their ether and ester, ethanol for example, ethylene glycol, glycol monomethyl ether or ethylene glycol monoethyl ether; Ketone, for example cyclohexanone; Intensive polar solvent, for example N-N-methyl-2-2-pyrrolidone N-; Dimethyl sulfoxide (DMSO) or dimethyl formamide, and rape oil or epoxidised rape oil, for example epoxidised cocoa butter or soya-bean oil; Or water.
Used solid-state carrier, what for example do the usefulness of dusting is general natural minerals filler, as calcite, talcum, kaolin, montmorillonite or U.S.'s atlapulgite.In order to improve its physical property, can add the silicic acid of high dispersion or the polymer absorbent of high dispersion.Suitable granulation absorbent carrier is a porous type, float stone for example, the brick of smashing, sepiolite or bentonite; The carrier of suitable non-absorption is the more such materials of calcite or sand.In addition, the inorganic or organic substance of a large amount of not granulations also can use, for example, and particularly dolomite or comminuted plants straw.
Be suitable for surface active cpd in the composition of the present invention for having well emulsify, dispersiveness and wettable non-ionic, cationic and/or anionic surfactant." surfactant " this speech also can be regarded as the mixture that comprises the kinds of surface activating agent.
The carrier and the batching that are fit to be used as in the composition of the present invention can be solid or liquid, are used for handling the soil of plant or plant growing or plant product with preparation, the material that particularly is used for handling the timber preparation is complementary, and these materials comprise, for example, natural or regenerate mineral materials, solvent, dispersant, surfactant, wetting agent, binder, intensifier, adhesive, fertilizer, antifreezing agent, repellant is with toner, anticorrosive, keep away aqua, desiccant, antiultraviolet stabilizing agent and other active component.
Suitable non-ionic surface active agent can be water miscible soap and water miscible synthetic surface active cpd.
Suitable soap comprises alkali metal salt, alkali salt or higher fatty acid (C unsubstituted or that replace
10-C
22) amine salt, for example oleic acid or stearic sodium salt or sylvite, perhaps the sodium salt of natural acid mixture or sylvite can obtain this natural acid from cocoa butter or tallow oil.In addition, also may mention the methyl tauride of fatty acid.
Yet, use so-called synthetic surfactant, particularly Zhi Fang sulfonate more frequently, the sulphate of fat, sulfonic acid acyl phenylimidazole derivative or alkylaryl sulfonate.The sulphate of the sulfonate of fat or fat is usually with alkali metal salt; the form of the amine salt of alkali salt or unsubstituted or replacement exists; and have an alkyl of a tool 8-22 carbon atom; said alkyl also has the such group of acyl group; the for example sodium salt of sulfonated oleic acid or calcium salt; lauryl sodium sulfate or dodecyl sulphate calcium, the sulfuric ester of the aliphatic alcohol that perhaps from natural acid, obtains.These compounds also comprise sulphate esters and fatty alcohol/oxirane addition sulfonate.Sulfonic acid acyl phenylimidazole derivative preferably contains the fatty acid group of 2 sulfonic groups and a tool 8-22 carbon atom.The example of alkylaryl sulfonate has sodium salt, calcium salt or the triethanolamine salt of DBSA, the sodium salt of dibutyl naphthalene sulfonic acids, calcium salt or triethanolamine salt, the perhaps sodium salt of naphthalene sulfonic acids/formal, calcium salt or triethanolamine salt.Corresponding phosphate also is suitable for, the phosphate ester salt of the oxirane of for example right-nonyl phenol and 4-14 mole or the additive compound of phosphatide.
Preferred nonionic is the derivative of polyglycol ether aliphatic series or cycloaliphatic alcohol, or the derivative of the polyglycol ether of fatty acid that replace or non-replacement and alkyl phenol, said derivative contains the group of 3-10 glycol ether, it is at the carbonyl moiety 8-20 of an aliphatic series carbon atom, at the moieties of alkyl phenol 6-18 carbon atom is arranged.
More suitably non-ionic surface active agent is the water-soluble addition product of PEO and polypropylene glycol and the amino polypropylene glycol of the ethylene that contains 1-10 carbon atom on alkyl chain, and this class addition product contains 20-250 ethylene glycol ether group and 10-100 propylene glycol group.This compounds contains a 1-5 ethylene glycol unit usually in each propane diols unit.
The representative example of non-ionic surface active agent has the nonyl phenol polyethoxy ethanol, castor oil polyglycol ether, polypropylene/PEO addition product, tributyl phenoxy group polyethoxy ethanol, polyethylene glycol and octylphenoxy polyethoxy ethanol.The fatty acid ester of polyethylene sorbierite, for example the polyoxyethylene sorbitol trioleate also is suitable non-ionic surface active agent.
Be used to improve that to use and reduce the useful especially additive of active component dosage be natural (animal or plant) or the synthetic noisy phosphatide or the phosphatide of lecithin class, phosphatidyl-ethanolamine for example, phosphatidylserine, phosphatidyl cerinic acid, lysolecithin, or cuorin.These phosphatide can obtain from animal or plant cell, particularly from brain, the heart or liver organization, obtain in yolk or the soybean.This class phosphatide that is fit to comprises lecithin mixture.Synthetic phosphatide, for example two octane lecithin and DPPCs.
Experimental section
Experiment 1: do the treatment processing by soaking medicine
With 10 μ g/ml, the DDAC (I) of 100 μ g/ml and 1000 μ g/ml prepares test water solution with the mould azoles (II-a) that presses down of 500 μ g/ml.Prepare the mixture that contains composition (I) and composition (II-a) with these test aqueous solutions, its ratio is respectively: (II-a) of (I) of 1000 μ μ g/ml and 500 μ g/ml; (II-a) of (I) of (II-a) of (I) of 100 μ g/ml and 500 μ g/ml and 10 μ μ g/ml and 500 μ g/ml.
The cork of a diameter 10mm is being contained 10
6Soak artificial infection later in the spore suspension of cfu/ml Penicillium digitatum (Penicillium digitatum) to lemon.After 24 hours lemon is immersed in 30 seconds in above-mentioned wherein a kind of test aqueous solution.
In 20 ℃ dark damp rooms, cultivated 14 days with untreated lemon that handle.Cultivate to finish the diameter that the fungus colony of growth is measured in the back, by efficient with the relatively calculating of contrast, i.e. percent inhibition.In millimeter, measure the girth and the distance between the girth of damaged area of the oese of 10mm diameter and come quantitative fungi growth.
With Limpel formula (Richter, D.L., Pestic.Sci.1987,19:309-315) the possible synergy of assessment: Ec=X+Y-[(X.Y)/100] the wherein addition reaction of Ec for expecting, or activity calculated, X is an observed control rate (%) when using composition A separately, and Y is an observed control rate (%) when using composition B separately.When two kinds of compositions are united viewed effect when using, or the activity that measures is then thought synergy has been taken place during greater than corresponding Ec value.
Table 1: DDAC (I) and but mould azoles (II-a) is prevented and treated Penicillium digitatum (Penicilliumdigitatum) on lemon effect (after cultivating 14 days)
| Compound | Experimental concentration (μ g/ml) | Effect (%) | Synergy (%) |
| DDAC(I) | 1000 | 22 | - |
| 100 | 0 | - | |
| 10 | 0 | - | |
| Press down mould azoles (II-a) | 500 | 78 | - |
| (I)+(II-a) | 1000+500 | 93 | 10 |
| 100+500 | 84 | 6 | |
| 10+500 | 91 | 3 | |
| Water (contrast) | - | 0 | - |
Experiment 2: malicious plate analysis
Measure the antifungal growth activity with malicious plate analysis method.With a kind of backbone solution (dimethyl sulphoxide solution that contains DDAC or Boscalid or fenhexamid or phonetic mould amine or thiophanate-methyl or fluorine bacterium azoles or Fluoxastrobin or ether bacterium amine or ZEN 90160 or pyraclostrobin through amount of calculation, concentration is 500ppm) be drawn onto on 24 orifice plates, make it through becoming the solution of final 0.21～5ppm after mixing with a kind of 12 steps of medium.Can use glucose agar medium (GA) (10g glucose, 1.5g K when doing experiment substrate with phonetic mould amine
2HPO
4, 2g KH
2PO
4, 1g (NH
4)
2SO
4, 0.5g MgSO
4With 1.25g agar, be dissolved in 1 liter of deionized water), can use potato dextrose agar medium (PDA) (4g potato medicinal extract, 20g bacto dextrose and 15g bacto agar are dissolved in 1 liter of deionized water) when doing experiment substrate with any other material.Inoculation 2 μ l spore/mycelium suspensions on medium.24 orifice plates are placed 22 ℃, the dark place of relative moisture 75%, one week the back pass judgment on fungi growth.
Following bacterial classification is used for malicious plate analysis experiment: Penicillium digitatum Sas strain (to suppressing the demethyl enzyme sensitivity of fungicide), Penicillium digitatum LSW930223 strain (reducing susceptibility) to the demethyl enzyme that suppresses fungicide, Italy mould H17 strain (reducing susceptibility) to the demethyl enzyme that suppresses fungicide, Botrytis cinerea bacterium BC03019 strain, geotrichum candidum bacterium, or the long spore bacterium A18 of white dish strain.
With the least concentration (ppm) of the institute's test compound that is enough to suppress the fungi visible growth or mixture as minimum inhibitory concentration (MIC).When not observing conk, represent with abbreviation " ng " in the table 2.Calculate synergistic size with described index of cooperation methods (F.C.Kull, P.C.Eismann, H.D.Sylvestrowicz, R.L.Mayer, 1961, Applied Microbiology9:538-541) such as von Kull.
Minimum inhibitory concentration value (MIC) when index of cooperation (SI)=(x/m)+(y/n)-m and n are respectively measured object 1 and 2 independent uses.-x and y are respectively the amount of measured object 1 and 2 in a kind of mixture that can suppress conk fully, and promptly x and y equal [amount in measured object 1 and 2 each comfortable mixture (for example 0.8 and 0.2,0.66 and 0.33 etc.)] and multiply by [the MIC value of mixture].If index of cooperation is 1, then synergy shows as a kind of addition.If this value shows a kind of synergy less than 1.
When a kind of MIC of compound value (5 are the highest experimental concentration) greater than 5 the time, then deciding its MIC value is 6.66 (than the high one-levels of dosage range), can calculate its index of cooperation SI with assurance).
Table 2: MIC value of the anti-fruit pathogen ash Portugal Portugal spore bacterium of fungicide (Botrytis cinerea) after DDAC and ripe fruit are plucked (minimum inhibitory concentration, the ppm of total active ingredient) and index of cooperation (SI)
*:, have no way of learning MIC, so can't calculate index of cooperation (SI) because experimental concentration is too low.Na: do not survey.
Claims (7)
1. composition, said composition comprises as the DDAC of composition (I), a kind of anti-fungal composition (II) and a kind of carrier that presses down mould azoles (II-a) that be selected from of handling the results ensuing crop, wherein composition (I) is 1: 50 to 10: 1 with the weight ratio of composition (II), to produce collaborative antifungic action.
2. composition as claimed in claim 1, wherein composition (I) is 1: 50 to 2: 1 with the weight ratio of composition (II).
3. composition as claimed in claim 1 or 2, wherein the amount of composition (I) existence is 10～1000mg/L, the amount that composition (II) exists is 10～1000mg/L.
4. the purposes of avoiding the fungi infringement with each described composition protective plant or its soil for growth, fruits and seeds in the claim 1～3.
5. purposes as claimed in claim 4, wherein said purposes are the processing after fruit is gathered in the crops.
6. one kind prepares each described method for compositions in the claim 1～3, and wherein said composition has synergy, the method is characterized in that: composition (I) and composition (II) are closely mixed with carrier.
7. one kind for the combination product that uses simultaneously or sequentially, contains:
(a) a kind of contain as the composition of the DDAC of composition (I) and
(b) a kind of composition that contains composition (II), composition (II) are a kind of antifungal agents that is selected from the processing results ensuing crop that presses down mould azoles (II-a);
Composition (I) in the wherein said composition (a) and (b) in the weight ratio of composition (II) be 1: 50 to 10: 1, so that collaborative antifungic action to be provided.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04100400 | 2004-02-04 | ||
| EP04100400.3 | 2004-02-04 | ||
| PCT/EP2005/050463 WO2005074684A2 (en) | 2004-02-04 | 2005-02-03 | Synergistic antifungal ddac compositions |
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| CN1913777A CN1913777A (en) | 2007-02-14 |
| CN1913777B true CN1913777B (en) | 2011-05-25 |
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| US (1) | US8008230B2 (en) |
| EP (2) | EP1856977A3 (en) |
| JP (1) | JP4681565B2 (en) |
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| AT (1) | ATE371371T1 (en) |
| AU (1) | AU2005211204B2 (en) |
| BR (1) | BRPI0507461A (en) |
| CA (1) | CA2554236C (en) |
| DE (1) | DE602005002236T2 (en) |
| DK (1) | DK1713331T3 (en) |
| HK (1) | HK1103942A1 (en) |
| HR (1) | HRP20070539T3 (en) |
| IL (1) | IL177234A0 (en) |
| NO (1) | NO20063696L (en) |
| NZ (1) | NZ548691A (en) |
| PL (1) | PL1713331T3 (en) |
| RS (1) | RS50506B (en) |
| RU (1) | RU2361400C2 (en) |
| SI (1) | SI1713331T1 (en) |
| UA (1) | UA84733C2 (en) |
| WO (1) | WO2005074684A2 (en) |
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| EP2454939A1 (en) | 2010-11-18 | 2012-05-23 | Bayer CropScience AG | Post-harvest treatment |
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| WO2005074684A2 (en) | 2005-08-18 |
| WO2005074684A3 (en) | 2005-12-01 |
| US8008230B2 (en) | 2011-08-30 |
| RS50506B (en) | 2010-03-02 |
| EP1856977A3 (en) | 2008-02-13 |
| EP1856977A2 (en) | 2007-11-21 |
| HRP20070539T3 (en) | 2009-04-30 |
| AU2005211204A1 (en) | 2005-08-18 |
| DE602005002236T2 (en) | 2008-05-15 |
| BRPI0507461A (en) | 2007-07-10 |
| CN1913777A (en) | 2007-02-14 |
| NZ548691A (en) | 2009-08-28 |
| NO20063696L (en) | 2006-08-17 |
| JP2007523898A (en) | 2007-08-23 |
| US20070142410A1 (en) | 2007-06-21 |
| UA84733C2 (en) | 2008-11-25 |
| ATE371371T1 (en) | 2007-09-15 |
| AR048296A1 (en) | 2006-04-19 |
| RU2006131581A (en) | 2008-03-10 |
| DK1713331T3 (en) | 2008-02-04 |
| ZA200606471B (en) | 2008-01-30 |
| CA2554236C (en) | 2012-09-11 |
| IL177234A0 (en) | 2006-12-10 |
| SI1713331T1 (en) | 2008-02-29 |
| PL1713331T3 (en) | 2008-01-31 |
| EP1713331A2 (en) | 2006-10-25 |
| CA2554236A1 (en) | 2005-08-18 |
| JP4681565B2 (en) | 2011-05-11 |
| EP1713331B1 (en) | 2007-08-29 |
| DE602005002236D1 (en) | 2007-10-11 |
| AU2005211204B2 (en) | 2010-01-28 |
| RU2361400C2 (en) | 2009-07-20 |
| HK1103942A1 (en) | 2008-01-04 |
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